【作者】 陶海征；

【导师】 赵修建；

【作者基本信息】 武汉理工大学 ， 材料学， 2004， 博士

【摘要】 正文：由于在光开关、1.3μm稀土掺杂光纤放大器等通讯领域可能获得重要应用，Ga₂S₃-基硫卤玻璃的光学非线性属性和稀土掺杂后的光谱发射性能引起了人们广泛关注。基于同主族元素In和Ga化学性质的类似，可以推测In₂S₃-基硫卤玻璃也应该具有同样的潜在应用。但是，据本文作者所知，关于Ga₂S₃-基和In₂S₃-基硫卤玻璃结构与性能的研究文献极少，特别是关于In₂S₃-基硫卤玻璃的基础研究文献几乎没有。由于光学非线性属性以及掺入基础玻璃中的稀土离子光谱发射性能均与玻璃的微结构和基础性质有非常密切的关系，因此，上述硫卤玻璃的组成、结构与性能研究具有重要的理论意义和应用价值。 本文利用金相显微镜、X-射线衍射谱、X-射线光电子能谱、拉曼散射、综合热分析、紫外-可见-近红外光谱和红外光谱等技术对四个准三元体系GeS₂-Ga₂S₃-KCl、GeS₂-Ga₂S₃-CsCl、GeS₂-In₂S₃-KCl、GeS₂-In₂S₃-CsCl的组成、结构与性能关系进行了深入研究和分析，获得了下述主要结论： 首次确定了GeS₂-In₂S₃-KCl和GeS₂-In₂S₃-CsCl准三元体系的玻璃形成区； 通过探讨Cs⁺局部配位环境及其对Ga₂S_4/2Cl₂桥式单元的影响，首次成功解释了玻璃Ga₂S₃-2CsCl和桥式分子Ga₂S₆拉曼谱相似和变化的原因； 通过深入分析碱金属卤化物引入所产生的微结构单元变化、引入阳离子M⁺（M=K、Cs）的局部配位状态及其对微结构单元镓硫氯混合四面体GaS_4-xCl_x和共边镓硫氯混合四面体Ga₂S_4/2Cl₂的影响，成功地阐释了所研究准三元体系GeS₂-Ga₂S₃-K（Cs）Cl中各组成系列样品的拉曼谱归属和演变； 首次研究了准三元体系GeS₂-In₂S₃-K（Cs）Cl玻璃的拉曼谱，并通过探讨该准三元体系中可能形成的微结构单元、引入阳离子M⁺（M=K、Cs）的局部配位及其对微结构单元铟硫氯混合四面体InS_4-xCl_x和铟硫氯混合八面体InS_6-xCl_x的影响成功给出了各组成系列玻璃拉曼谱归属及演变的微结构缘由。 碱金属氯化物以下述方式进入玻璃微结构：阳离子M⁺是以Cl为最近邻配位的单壳层形式均匀分散于玻璃网络中；在碱金属氯化物掺杂的Ga₂S₃-基硫卤玻璃中，阴离子Cl^-通过形成镓硫氯混合四面体的方式进入玻璃网络；而在碱金属氯化物掺杂的In₂S₃-基硫卤玻璃中，阴离子Cl^-则是通过形成铟硫氯混合多面体(主要是铟硫氯混合四面体InS_4-xCl_x和少量铟硫氯混合八面体InS_6-xCl_x)的方式进入玻璃网络； 随着碱金属氯化物含量增加，玻璃的Urbach吸收边逐渐向短波方向移动、红外透过截至波长基本上没有发生变化、玻璃转变温度下降、耐水性变差； GeS₂-Ga（In）₂S₃-CsCl准三元体系中由于引入CsCl使微结构发生变化，导致了电子态密度的变化，从而使Urbach吸收边随样品组成变化而发生移动；并根据CsCl引入对玻璃微观结构单元影响的分析解释了CsCl掺量增加使玻璃耐水性下降的原因； GeS₂-Ga（In）₂S₃-KCl准三元体系中，具有最佳玻璃形成能力的玻璃组成分别为：0.6GeS₂-0.2Ga₂S₃-0.2KCl、0.7GeS₂-0.15In₂S₃-0.15KCl。更多还原

【Abstract】 Content: Recently Ga2S3-based chalcohalide glasses have attracted much attention according to their possible applications such as ultra-fast all optical switching, rare-earth doped 1.3um fiber amplifier, and etc. In addition, based on the similarity of chemical properties with Ga and In, it can be anticipated that ln2S3-based Chalcohalide glasses also be the leading candidates in the above-mentioned fields. However, to our knowledge, there are few reports about Ga2S3-based especially In2S3-based chalcohalide glasses. Considering the intimate relation among the above-mentioned applications, microstructure and basic properties of materials, understanding and utilization of the basic studying findings are worthwhile from theoretical and practical viewpoints.Utilizing the techniques such as X-Ray diffraction, Raman spectra, Comprehensive thermal analysis, UV-Vis-Near IR and FTIR, and etc., probing and analysis has been made systematically about the relationships of composition, structure and properties within four pseudo-ternary systems: GeS2-Ga2S3-KCl, GeS2-Ga2S3-CsCl, GeS2-In2S3-KCI and GeS2-In2S3-CsCI. The obtained conclusions are as follows:The glass-forming regions within GeS2-In2S3-K(Cs)Cl systems were reported firstly.Similarities and changes of Raman spectra between GaS CsCI glass and bridged molecular Ga2Cl6 were ascribed successfully based on the local surroundings of Cs+and its influence on bridged units Ga2S6-xCIx.Ascriptions and evolutions of Raman spectra within GeS2-Ga2S3-K (Cs) Cl systems were made reasonably in terms of micro-structural variation originating from the introduction of MCI (M=K,Cs) such as: local surroundings of M+ ions and its effect on mixed tetrahedral GaS4-xClx together with edge-shared tetrahedral Ga2S6-xClx.Raman spectra of samples within GeS2-In2S3-K(Cs)Cl systems were reported for the first time. Furthermore, assignments and shifts of spectra on every component serial had been elucidated reasonably according to micro-structural transformation resulting from composition changes.Among the glassy micro-structural network, alkali chlorine MCl(M=K,Cs) exists as the flowing forms: M* ions as Cl for its nearest coordination; Cl atoms enter into glassy network as tetrahedral GaS4.xClx within GeS2-Ga2S3-K (Cs) Cl systems; while Cl atoms enter into amorphous net as tetrahedral(InS4.xClx;mainly)and octahedral (InS6-xClx;lessly) units within GeS2-In2S3-K(Cs)CI systems.With the increase of MCI amount, there is a shift toward shorter wavelength about glassy Urbach absorption edge; a decline of glass transition temperature; and a drop on glassy water-resistance within the above-mentioned four systems.Within GeS2-Ga(In)2S3-CsCI systems, the shift about Urbach absorption edge was reasonably ascribed inspiring from the effect of CsCI on the electronic DOS(density of States); and the descending of water-resistance following the increase of CsCI content was explained successfully based on the effect of CsCI on glassy micro-structural units.Originating from the research of comprehensive thermal properties about the two pseudo-ternary systems: GeS2-Ga(ln)2S3-KCI, the compositions having the best glass-forming abilities were found out: 0.6GeS2-0.2Ga2S3-0.2K.CI 0.7GeS2-0.15In2S3-0.15KCI.更多还原